Investigating Cu(0)‐Mediated Polymerizations: New Kinetic Insights Based on a Comparison of Kinetic Modeling with Experimental Data

A kinetic model is developed mimicking experimental results obtained via detailed kinetic investigation of Cu0‐mediated LRP processes of butyl acrylate in variable solvents at 50 °C. In all polymerizations, a pronounced offset in the M̄ _ n versus conversion profile is observed. The kinetic modeling predicts that conventional FRP is responsible for a high molecular weight fraction of terminated polymer. The initial M̄ _ n offset is congruent with a relatively slow establishment of the controlling equilibrium. Kinetic modeling and experiments demonstrate that the conversion versus time data cannot be adequately described by a first‐order kinetic analysis. For selected rate coefficients (ka, kd, and kdis_cu) a range is assigned, which affords a well controlled polymerization. magnified image